The authors investigated the process of cultural adjustment among 13 Korean immigrant youths using consensual qualitative research (C. E. Hill, B. J. Thompson, & E. N. Williams, 1997). Results indicate that Korean youth are expected to negotiate and shift their identities to meet differing expectations across various interpersonal contexts. Participants also report struggling to balance “American” and “Korean” cultural values and norms and to use social support networks, such as family and friends, to deal with the stress of acculturation.
A new streamlined and scaled divergent total synthesis of pocket-modified vancomycin analogs is detailed that provides a common late-stage intermediate [Ψ[C(�S)NH]Tpg 4 ]vancomycin (LLS = 18 steps, 12% overall yield, >5 g prepared) to access both existing and future pocket modifications. Highlights of the approach include an atroposelective synthesis of [Ψ[C(�S)NH]Tpg 4 ]vancomycin aglycon (11), a one-pot enzymatic glycosylation for direct conversion to [Ψ[C(�S)NH]Tpg 4 ]vancomycin ( 12), and new powerful methods for the late-stage conversion of the embedded thioamide to amidine/aminomethylene pocket modifications. Incorporation of two peripheral modifications provides a scalable total synthesis of the maxamycins, all prepared from aglycon 11 without use of protecting groups. Thus, both existing and presently unexplored pocket-modified analogues paired with a range of peripheral modifications are accessible from this common thioamide intermediate. In addition to providing an improved synthesis of the initial member of the maxamycins, this is illustrated herein with the first synthesis and examination of maxamycins that contain the most effective of the pocket modifications (amidine) described to date combined with two additional peripheral modifications. These new amidine-based maxamycins proved to be potent, durable, and efficacious antimicrobial agents that display equipotent activity against vancomycin-sensitive and vancomycin-resistant Gram-positive organisms and act by three independent synergistic mechanisms of action. In the first such study conducted to date, one new maxamycin (21, MX-4) exhibited efficacious in vivo activity against a feared and especially challenging multidrug-resistant (MRSA) and vancomycin-resistant (VRSA) S. aureus bacterial strain (VanA VRS-2) for which vancomycin is inactive.
An efficient generation method of didehydroisobenzofuran, a new heteroaryne species, was developed by bromine/lithium exchange of the dibromoisobenzofuran. The reactive intermediate, thus generated, was trapped by appropriate arynophile to give the [2+2], [2+3], and [2+4] cycloadducts, respectively. Moreover, the reaction could be applied to the syntheses of isoanthracenofurans (anthra[2,3‐c]furans), a new class of heteroacenes, with isoelectoronic structure to the corresponding acenoheteroles (anthra[2,3‐b]furans).
All reactions utilizing air-or moisture-sensitive reagents were performed in dried glassware under an atmosphere of dry argon. Ethereal solvents, dichloromethane, and toluene (anhydrous; Kanto Chemical Co., Inc.) were used as received. Other reagents were used without further purification as received from commercial. For thin-layer chromatography (TLC) analysis, Merck pre-coated plates (TLC silica gel 60 F 254 , Art 5715, 0.25 nm) were used. Silica-gel preparative thin-layer chromatography (PTLC) was performed using plates prepared from Merck silica gel 60 PF 254 (Art 7747). For flash column chromatography, silica gel 60N (Spherical, neutral, 63-210 µm) from Kanto Chemical was used. Higher-accuracy purifications were performed by Smart Flash EPCLC W-Prep "XY system (YMAZEN SCIENCE, Inc.) equipped with the UV detector (prep UV-254W). High-flash L column (silicagel 40 µm, 34 g, 26 x 100 mm), High-flash 2L column (silicagel, 40 µm, 45 g, 26 x 150 mm), and Ultra-Pack C (SiOH 40 µm 60 Å, 195 g, 37 x 300 mm) were used. Melting point (mp) determinations were performed using a Yanaco MP-500 instrument or a METTLER TOLEDO MP 70 melting point system, and are uncorrected. 1H-and 13C-NMR were measured on a JEOL ECX-400 (400 MHz), or a Bruker Avance III 600 (600MHz) spectrometer in the solvent indicated; Chemical shifts (δ) are expressed in parts per million (ppm) downfield from internal standard (tetramethylsilane, 0.00 ppm), and coupling constants (J) are reported as hertz (Hz). Splitting patterns are indicated as follows: s = singlet, d = doublet, t = triplet, q = quartet, sept = septet, m = multiplet, br = broad. Infrared (IR) spectra were recorded on a Thermo Fisher SCIENTIFIC NICOLET iS5 FTIR spectrometer. Elemental analyses were recorded on an Elementar vario MICRO cube analyzer. Highperformance liquid chromatography (HPLC) analyses were performed by using a Jasco 880PU instrument with UV detection at 254 or 300 nm. High-resolution mass spectra (HRMS) were obtained with Bruker Kaltonics microTOF-Q II. Optical rotations ([α] D) were measured on a Jasco DIP-1000 polarimeter. ! S5 Synthesis of side chain 11 In a two-necked round-bottom flask was placed LiCl (985 mg, 6.92 mmol), to which a solution of sulfinyl phosphonate 6 (2.21 g, 6.92 mmol) in MeCN (36 mL) and DBU (2.06 mL, 13.8 mmol) was added successively at room temperature. The mixture was stirred for 5min and I 2 (1.76 g, 6.92 mmol) was added in several portions. The mixture turned into an orange color solution. After stirring for 10 min, a solution of aldehyde 9 (739 mg, 4.61 mmol) in MeCN (10 mL) was slowly dropwised and the stirring was continued for 5 min at room temperature. The reaction mixture was quenched with 10% Na 2 S 2 O 3 aqueous solution, extracted with EtOAc (x3) and the combined organic extracts were washed with brine, sat. NaHCO 3 aqueous solution, dried (Na 2 SO 4), and concentrated in vacuo. The residue was purified by flash column chromatography (silica gel, hexane/EtOAc=3/2) to afford vinyl sulfoxide 11 (1.48 g, 76%, E/Z = 97/3) as a yellow oil.
Stereodefined α-iodovinyl sulfoxides bearing a sulfinyl group and an iodo group were prepared by a one-pot iodination/Horner-Wadsworth-Emmons reaction protocol. This reaction can be applied to a wide range of aldehydes, and further application was demonstrated.
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